Halogenated polymers with new sequence distributions

• US 7,491,773 B2
• Filed: 12/10/2004
• Issued: 02/17/2009
• Est. Priority Date: 12/20/2002
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Chung, David Yen-Lung, Shaffer, Timothy Daniel
• Primary Examiner(s): RABAGO, ROBERTO
• Application Number:
  US11/009,660
• Publication Number:
  US 20050101751A1
• Time in Patent Office: 1,530 Days
• Field of Search: 525/192, 525/232, 525/332.3, 525/332.8, 525/333.1, 525/355
• US Class Current: 525/332.3
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/002 Scale prevention in a polymerisation reactor or its auxiliary parts
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 2/14 Organic medium
• CPC Class Codes: C08F 210/12 with conjugated diolefins, e.g. butyl rubber
• CPC Class Codes: C08F 236/08 Isoprene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 4/00 Polymerisation catalysts
• CPC Class Codes: C08F 4/06 Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
• CPC Class Codes: C08F 4/12 of boron, aluminium, gallium, indium, thallium or rare earths
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence

Abstract

The invention relates to new polymerization processes including diluents including hydrofluorocarbons and their use to produce novel halogenated polymers with new sequence distributions. In particular, the invention relates to halogenated copolymers of an isoolefin, preferably isobutylene, and a multiolefin, preferably a conjugated diene, more preferably isoprene, with new sequence distributions.

Claims

1. A halogenated copolymer comprising an isoolefin and a multiolefin, the halogenated copolymer having a copolymer sequence distribution defined by the following equation:

F=mA/(1=mA)²

wherein m is the copolymer sequence distribution parameter;

A is the molar ratio of multiolefin to isoolefin in the copolymer; and

F is the isoolefin-multiolefin-multiolefin triad fraction in the copolymer;

wherein m is from greater than 2.5; and

wherein m is determined by solving said equation.

2. The halogenated copolymer of claim 1, wherein m is from greater than 3.5.

3. The halogenated copolymer of claim 1, wherein the multiolefin is a conjugated diene.

4. The halogenated copolymer of claim 1, wherein the multiolefin content is from greater than 0.5 mol%.

5. The halogenated copolymer of claim 1, wherein the multiolefin content is from greater than 1.0 mol%.

6. The halogenated copolymer of claim 1, wherein the multiolefin content is from greater than 2.5 mol%.

7. The halogenated copolymer of claim 1, wherein the multiolefin content is from greater than 5.0 mol%.

77. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer is halogenated with chlorine or bromine.

78. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogen content is greater than 0.5 wt% to based upon the weight of the halogenated copolymer.

79. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogen content is from 0.5 wt% to 3.0 wt% based upon the weight of the halogenated copolymer.

80. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a Mw of from greater than 50,000.

81. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a Mw of from greater than 100,000.

82. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a Mw of from greater than 500,000.

83. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a MWD of from greater than 2.

84. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a MWD of from 2 to 6.

85. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a Mooney viscosity of at least 20 ±

5 (ML 1 +8 at 125°

C., ASTM D

     1646).

86. The halogenated copolymer of claim 1, 8, 14, 23, or 31, wherein the halogenated copolymer has a Mooney viscosity of from 20 ±

5 to 60 ±

5 (ML 1 +8 at 125°

C., ASTM D

     1646).

87. A blend comprising the halogenated copolymer of claim 1, 8, 14, 23, or 31 and a secondary rubber independently selected from the group consisting of at least one of natural rubber, polyisoprene rubber, poly(styrene-co-butadiene) rubber (SBR), polybutadiene rubber (BR), poly(isoprene-co-butadiene) rubber (IBR), styrene-isoprene -butadiene rubber (SIBR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), polysulfide, isobutylene/cyclopentadiene copolymer rubber, isobutylene/methyl cyclopentadiene copolymer rubber, nitrile rubber, propylene oxide polymers, star-branched butyl rubber and halogenated star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, star-branched brominated butyl (polyisobutylene/isoprene copolymer) rubber;

poly(isobutylene-co-p-methylstyrene) and halogenated poly(isobutylene-co-p -methylstyrene), halogenated poly(isobutylene-co-isoprene-co-p-methylstyrene), poly(isobutylene-co-isoprene-co-styrene), halogenated poly(isobutylene-co-isoprene-co -styrene), poly(isobutylene-co-isoprene-co-α

-methylstyrene) halogenated poly(isobutylene-co-isoprene-co-α

-methylstyrene), and mixtures thereof.

8. A halogenated copolymer comprising isobutylene and isoprene, the halogenated copolymer having a copolymer sequence distribution defined by the following equation:

F=mA/(1=mA)²

wherein m is the copolymer sequence distribution parameter;

A is the molar ratio of isoprene to isobutylene in the copolymer; and

F is the isobutylene-isoprene-isoprene triad fraction in the copolymer;

wherein m is from greater than 2.5; and

wherein m is determined by solving said equation.

9. The halogenated copolymer of claim 8, wherein m is from greater than 3.5.

10. The halogenated copolymer of claim 8, wherein the isoprene content is from greater than 0.5 mol%.

11. The halogenated copolymer of claim 8, wherein the isoprene content is from greater than 1.0 mol%.

12. The halogenated copolymer of claim 8, wherein the isoprene content is from greater than 2.5 mol%

13. The halogenated copolymer of claim 8, wherein the isoprene content is from greater than 5.0 mol%

14. A halogenated copolymer comprising an isoolefin and a multiolefin, the halogenated copolymer having a copolymer sequence distribution defined by the following equation:

F =m A / (1=mA)²

wherein m is the copolymer sequence distribution parameter;

A is the molar ratio of multiolefin to isoolefin in the copolymer; and

F is the isoolefin-multiolefin-multiolefin triad fraction in the copolymer;

wherein m is from 1.10 to 1.25; and

wherein m is determined by solving said equation.

15. The halogenated copolymer of claim 14, wherein m is from 1.15 to 1.20.

16. The halogenated copolymer of claim 14, wherein m is from 1.15 to 1.25.

17. The halogenated copolymer of claim 14, wherein m is about 1.20.

18. The halogenated copolymer of claim 14, wherein the multiolefin is a conjugated diene.

19. The halogenated copolymer of claim 14, wherein the multiolefin content is from greater than 0.5 mol%.

20. The halogenated copolymer of claim 14, wherein the multiolefin content is from greater than 1.0 mol%.

21. The halogenated copolymer of claim 14, wherein the multiolefin content is from greater than 2.5 mol%.

22. The halogenated copolymer of claim 14, wherein the multiolefin content is from greater than 5.0 mol%.

23. A halogenated copolymer comprising isobutylene and isoprene, the halogenated copolymer having a copolymer sequence distribution defined by the following equation:

F =m A / (1=mA)²

wherein m is the copolymer sequence distribution parameter;

A is the molar ratio of isoprene to isobutylene in the copolymer; and

F is the isobutylene-isoprene-isoprene triad fraction in the copolymer;

wherein m is from 1.10 to 1.25; and

wherein m is determined by solving said equation.

24. The halogenated copolymer of claim 23, wherein m is from 1.15 to 1.20.

25. The halogenated copolymer of claim 23, wherein m is from 1.15 to 1.25.

26. The halogenated copolymer of claim 23, wherein m is about 1.20.

27. The halogenated copolymer of claim 23, wherein the isoprene content is from greater than 0.5 mol%.

28. The halogenated copolymer of claim 23, wherein the isoprene content is from greater than 1.0 mol%.

29. The halogenated copolymer of claim 23, wherein the isoprene content is from greater than 2.5 mol%.

30. The halogenated copolymer of claim 23, wherein the isoprene content is from greater than 5.0 mol%.

31. A halogenated copolymer produced by the process comprising contacting an isoolefin and a multiolefin, one or more Lewis acid(s), one or more initiator(s), and a diluent comprising one or more hydrofluorocarbon(s) (HFC'"'"'s);

the halogenated copolymer having a copolymer sequence distribution defined by the following equation;

F =m A / (1=mA)²

wherein m is the copolymer sequence distribution parameter;

A is the molar ratio of multiolefin to isoolefin in the copolymer; and

F is the isoolefin-multiolefin-multiolefin triad fraction in the copolymer;

wherein m is from greater than 2.5 or m is from 1.10 to 1.25; and

wherein m is determined by solving said equation.

32. The halogenated copolymer of claim 31, wherein m is from greater than 3.5.

33. The halogenated copolymer of claim 31, wherein m is from 1.15 to 1.20.

34. The halogenated copolymer of claim 31, wherein m is from 1.15 to 1.25.

35. The halogenated copolymer of claim 31, wherein m is about 1.20.

36. The halogenated copolymer of claim 31, wherein the multiolefin is isoprene and the isoolefin is isobutylene.

37. The halogenated copolymer of claim 31, wherein the multiolefin content is from greater than 0.5 mol%.

38. The halogenated copolymer of claim 31, wherein the multiolefin content is from greater than 1.0 mol%.

39. The halogenated copolymer of claim 31, wherein the multiolefin content is from greater than 2.5 mol%.

40. The halogenated copolymer of claim 31, wherein the multiolefin content is from greater than 5.0 mol%.

41. The halogenated copolymer of claim 31, wherein one or more hydrofluorocarbon(s) is represented by the formula:

C_xH_yF_z wherein x is an integer from 1 to 40 and y and z are integers of one or more.

42. The halogenated copolymer of claim 41, wherein x is from 1 to 10.

43. The halogenated copolymer of claim 41, wherein x is from 1 to 6.

44. The halogenated copolymer of claim 41, wherein x is from 1 to 3.

45. The halogenated copolymer of claim 31, wherein the one or more hydrofluorocarbon(s) is independently selected from the group consisting of fluoromethane;

difluoromethane;

trifluoromethane;

fluoroethane;

1,1 -difluoroethane;

1,2-difluoroethane;

1,1,1 -trifluoroethane;

1,1,2-trifluoroethane;

1,1,1,2-tetrafluoroethane;

1,1,2,2-tetrafluoroethane;

1,1,1,2,2-pentafluoroethane;

1 -fluoropropane;

2-fluoropropane;

1,1 -difluoropropane;

1,2-difluoropropane;

1,3-difluoropropane;

2,2-difluoropropane;

1,1,1 -trifluoropropane;

1,1,2-trifluoropropane;

1,1,3 -trifluoropropane;

1,2,2-trifluoropropane;

1,2,3 -trifluoropropane;

1,1,1,2-tetrafluoropropane;

1,1,1,3-tetrafluoropropane;

1,1,2,2-tetrafluoropropane;

1,1,2,3 -tetrafluoropropane;

1,1,3,3-tetrafluoropropane;

1,2,2,3-tetrafluoropropane;

1,1,1,2,2-pentafluoropropane;

1,1,1,2,3-pentafluoropropane;

1,1,1,3,3 -pentafluoropropane;

1,1,2,2,3 -pentafluoropropane;

1,1,2,3,3-pentafluoropropane;

1,1,1,2,2,3-hexafluoropropane;

1,1,1,2,3,3;

-hexafluoropropane;

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,2,3,3-heptafluoropropane;

1,1,1,2,3,3,3-heptafluoropropane;

1 -fluorobutane;

2-fluorobutane;

1,1 -difluorobutane;

1,2-difluorobutane;

1,3 -difluorobutane;

1 ,4-difluorobutane;

2,2-difluorobutane;

2,3-difluorobutane;

1,1,1 -trifluorobutane;

1,1,2-trifluorobutane;

1,1,3 -trifluorobutane;

1,1,4-trifluorobutane;

1,2,2-trifluorobutane;

1,2,3 -trifluorobutane;

1,3,3 -trifluorobutane;

2,2,3-trifluorobutane;

1,1,1,2-tetrafluorobutane;

1,1,1,3 -tetrafluorobutane;

1,1,1,4-tetrafluorobutane;

1,1,2,2-tetrafluorobutane;

1,1,2,3 -tetrafluorobutane;

1,1,2,4-tetrafluorobutane;

1,1,3,3 -tetrafluorobutane;

1,1,3,4-tetrafluorobutane;

1,1,4,4-tetrafluorobutane;

1,2,2,3 -tetrafluorobutane;

1,2,2,4-tetrafluorobutane;

1,2,3,3-tetrafluorobutane;

1,2,3,4-tetrafluorobutane;

2,2,3,3-tetrafluorobutane;

1,1,1,2,2-pentafluorobutane;

1,1,1,2,3-pentafluorobutane;

1,1,1,2,4-pentafluorobutane;

1,1,1,3,3-pentafluorobutane;

1,1,1,3,4-pentafluorobutane;

1,1,1,4,4-pentafluorobutane;

1,1,2,2,3-pentafluorobutane;

1,1,2,2,4-pentafluorobutane;

1,1,2,3,3-pentafluorobutane;

1,1,2,4,4-pentafluorobutane;

1,1,3,3,4-pentafluorobutane;

1,2,2,3,3-pentafluorobutane;

1,2,2,3,4-pentafluorobutane;

1,1,1,2,2,3-hexafluorobutane;

1,1,1,2,2,4-hexafluorobutane;

1,1,1,2,3,3 -hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;

1,1,1,2,4,4-hexafluorobutane;

1,1,1,3,3,4-hexafluorobutane;

1,1,1,3,4,4-hexafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,1,2,2,3,3 -hexafluorobutane;

1,1,2,2,3,4-hexafluorobutane;

1,1,2,2,4,4-hexafluorobutane;

1,1,2,3,3,4-hexafluorobutane;

1,1,2,3,4,4-hexafluorobutane;

1,2,2,3,3,4-hexafluorobutane;

1,1,1,2,2,3,3-heptafluorobutane;

1,1,1,2,2,4,4-heptafluorobutane;

1,1,1,2,2,3,4-heptafluorobutane;

1,1,1,2,3,3,4-heptafluorobutane;

1,1,1,2,3,4,4-heptafluorobutane;

1,1,1,2,4,4,4-heptafluorobutane;

1,1,1,3,3,4,4-heptafluorobutane;

1,1,1,2,2,3,3,4-octafluorobutane;

1,1,1,2,2,3,4,4-octafluorobutane;

1,1,1,2,3,3,4,4-octafluorobutane;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,2,3,4,4,4-octafluorobutane;

1,1,1,2,2,3,3,4,4-nonafluorobutane;

1,1,1,2,2,3,4,4,4-nonafluorobutane;

1-fluoro-2-methylpropane;

1,1-difluoro-2-methylpropane;

1,3-difluoro-2-methylpropane;

1,1,1 -trifluoro-2-methylpropane;

1,1,3 -trifluoro-2-methylpropane;

1,3-difluoro-2-(fluoromethyl)propane;

1,1,1,3 -tetrafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-methylpropane;

1,1,3 -trifluoro -2-(fluoromethyl)propane;

1,1,1,3,3 -pentafluoro-2-methylpropane;

1,1,3,3 -tetrafluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-(fluoromethyl)propane;

fluorocyclobutane;

1,1 -difluorocyclobutane;

1,2-difluorocyclobutane;

1,3-difluorocyclobutane;

1,1,2-trifluorocyclobutane;

1,1,3 -trifluorocyclobutane;

1,2,3 -trifluorocyclobutane;

1,1,2,2-tetrafluorocyclobutane;

1,1,3,3 -tetrafluorocyclobutane;

1,1,2,2,3-pentafluorocyclobutane;

1,1,2,3,3 -pentafluorocyclobutane;

1,1,2,2,3,3 -hexafluorocyclobutane;

1,1,2,2,3,4-hexafluorocyclobutane;

1,1,2,3,3,4-hexafluorocyclobutane;

1,1,2,2,3,3,4-heptafluorocyclobutane;

vinyl fluoride;

1,1 -difluoroethene;

1,2-difluoroethene;

1,1,2-trifluoroethene;

1 -fluoropropene, 1,1 -difluoropropene;

1,2-difluoropropene;

1,3-difluoropropene;

2,3-difluoropropene;

3,3 -difluoropropene;

1,1,2-trifluoropropene;

1,1,3-trifluoropropene;

1,2,3-trifluoropropene;

1,3,3 -trifluoropropene;

2,3,3 -trifluoropropene;

3,3,3-trifluoropropene;

1 -fluoro- 1 -butene;

2-fluoro- 1 -butene;

3 -fluoro-1 -butene;

4-fluoro -1 -butene;

1,1 -difluoro-1 -butene;

1,2-difluoro- 1 -butene;

1,3 -difluoropropene;

1,4-difluoro -1-butene;

2,3-difluoro-1-butene;

2,4 -difluoro- 1 -butene;

3,3 -difluoro-1 -butene;

3,4-difluoro-1 -butene;

4,4-difluoro-1 -butene;

1,1,2-trifluoro-1 -butene;

1,1,3 -trifluoro-1-butene;

1,1,4-trifluoro-1 -butene;

1,2,3-trifluoro-1 -butene;

1,2,4-trifluoro-1 -butene;

1,3,3-trifluoro-1 -butane;

1,3,4-trifluoro-1 -butene;

1,4,4-trifluoro-1 -butene;

2,3,3 -trifluoro-1-butene;

2,3,4-trifluoro-1 -butene;

2,4,4-trifluoro-1 -butene;

3,3,4-trifluoro-1 -butene;

3,4,4-trifluoro-1 -butene;

4,4,4-trifluoro- 1 -butene;

1,1,2,3 -tetrafluoro- 1 -butene;

1,1,2,4-tetrafluoro-1 -butene;

1,1,3,3-tetrafluoro-1 -butene;

1,1,3,4-tetrafluoro- 1 -butene;

1,1,4,4-tetrafluoro-1 -butene;

1,2,3,3-tetrafluoro-1 -butene;

1,2,3,4-tetrafluoro- 1 -butene;

1,2,4,4-tetrafluoro-1 -butene;

1,3,3,4-tetrafluoro-1 -butene;

1,3,4,4-tetrafluoro- 1 -butene;

1,4,4,4-tetrafluoro-1 -butene;

2,3,3,4-tetrafluoro-1 -butene;

2,3,4,4-tetrafluoro- 1 -butene;

2,4,4,4-tetrafluoro-1 -butene;

3,3,4,4-tetrafluoro-1 -butene;

3,4,4,4-tetrafluoro- 1 -butene;

1,1,2,3,3-pentafluoro-1 -butene;

1,1,2,3,4-pentafluoro-1 -butene;

1,1,2,4,4-pentafluoro-1 -butene;

1,1,3,3,4-pentafluoro-1 -butene;

1,1,3,4,4-pentafluoro-1 -butene;

1,1,4,4,4-pentafluoro-1-butene;

1,2,3,3,4-pentafluoro-1 -butene;

1,2,3,4,4-pentafluoro-1 -butene;

1,2,4,4,4-pentafluoro-1 -butene;

2,3,3,4,4-pentafluoro-1 -butene;

2,3,4,4,4-pentafluoro-1 -butene;

3,3,4,4,4-pentafluoro-1 -butene;

1,1,2,3,3,4-hexafluoro-1 -butene;

1,1,2,3,4,4-hexafluoro -1 -butene;

1,1,2,4,4,4-hexafluoro-1 -butene;

1,2,3,3,4,4-hexafluoro-1 -butene;

1,2,3,4,4,4-hexafluoro-1 -butene;

2,3,3,4,4,4-hexafluoro-1 -butene;

1,1,2,3,3,4,4-heptafluoro-1 -butene;

1,1,2,3,4,4,4-heptafluoro-1-butene;

1,1,3,3,4,4,4-heptafluoro-1-butene;

1,2,3,3,4,4,4-heptafluoro-1 -butene;

1 -fluoro-2-butene;

2-fluoro-2-butene;

1,1 -difluoro-2-butene;

1,2-difluoro-2-butene;

1,3 -difluoro-2-butene;

1,4-difluoro-2-butene;

2,3 -difluro-2-butene;

1,1,1 -trifluoro-2-butene;

1,1,2-trifluoro-2-butene;

1,1,3 -trifluoro-2-butene;

1,1,4-trifluoro -2-butene;

1,2,3-trifluoro-2-butene;

1 ,2,4-trifluoro-2-butene;

1,1,1,2-tetrafluoro-2-butene;

1,1,1,3 -tetrafluoro-2-butene;

1,1,1,4-tetrafluoro-2-butene;

1,1,2,3 -tetrafluoro-2-butene;

1,1,2,4-tetrafluoro-2-butene;

1,2,3,4-tetrafluoro-2-butene;

1,1,1,2,3 -pentafluoro-2-butene;

1,1,1,2,4-pentafluoro-2-butene;

1,1,1,3,4-pentafluoro-2-butene;

1,1,1,4,4-pentafluoro-2-butene;

1,1,2,3,4-pentafluoro-2-butene;

1,1,2,4,4-pentafluoro-2-butene;

1,1,1,2,3,4-hexafluoro-2-butene;

1,1,1,2,4,4-hexafluoro-2-butene;

1,1,1,3,4,4-hexafluoro-2-butene;

1,1,1,4,4,4-hexafluoro-2-butene;

1,1,2,3,4,4-hexafluoro-2-butene;

1,1,1,2,3,4,4-heptafluoro-2-butene;

1,1,1,2,4,4,4-heptafluoro-2-butene; and

mixtures thereof.

46. The halogenated copolymer of claim 31, wherein the one or more hydrofluorocarbon(s) is independently selected from the group consisting of fluoromethane, difluoromethane, trifluoromethane, 1,1 -difluoroethane, 1,1,1 -trifluoroethane, 1,1,1,2-tetrafluoroethane, and mixtures thereof.

47. The halogenated copolymer of claim 31, wherein the diluent comprises from 15 to 100 volume % HFC based upon the total volume of the diluent.

48. The halogenated copolymer of claim 31, wherein the diluent comprises from 20 to 100 volume % HFC based upon the total volume of the diluent.

49. The halogenated copolymer of claim 31, wherein the diluent comprises from 25 to 100 volume % HFC based upon the total volume of the diluent.

50. The halogenated copolymer of claim 31, wherein the diluent further comprises a hydrocarbon, a non-reactive olefin, and/or an inert gas.

51. The halogenated copolymer of claim 31, wherein the diluent further comprises a halogenated hydrocarbon other than an HFC.

52. The halogenated copolymer of claim 51, wherein the halogenated hydrocarbon is methyl chloride.

53. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MX₄;

wherein M is a Group 4,5,or 14 metal; and

each X is a halogen.

54. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MR_nX₄₋

n;

wherein M is Group 4,5,or 14 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4; and

each X is a halogen.

55. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>4−

(m+n)</sub>;

wherein M is Group 4,5,or 14 metal;

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4, wherein the sum of n and m is not more than 4; and

each X is a halogen.

56. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RC=OO)_nR′

_mX<sub>4−

(m+n)</sub>;

wherein M is Group 4,5,or 14 metal;

each RC=OO is a monovalent C₂ to C₃₀ hydrocarbacyl radical independently selected from the group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4, wherein the sum of n and m is not more than 4; and

each X is a halogen.

57. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MOX₃;

wherein M is a Group 5 metal; and

each X is a halogen.

58. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MX₃;

wherein M is a Group 13 metal; and

each X is a halogen.

59. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MR_nX₃₋

n;

wherein M is a Group 13 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 1 to 3; and

each X is a halogen.

60. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>3−

(m+n)</sub>;

wherein M is a Group 13 metal;

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 3;

m is an integer from 0 to 3, wherein the sum of n and m is from 1 to 3; and

each X is a halogen.

61. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RC=OO)_nR′

_mX<sub>3−

(m+n)</sub>;

wherein M is a Group 13 metal;

each RC=OO is a monovalent hydrocarbacyl radical independently selected from the C₂ to C₃₀ group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 3;

m is a integer from 0 to 3, wherein the sum of n and m is from 1 to 3; and

each X is a halogen.

62. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MX_y;

wherein M is a Group 15 metal;

each X is a halogen; and

y is 3,4 or 5.

63. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula MR_nX_y−

n;

wherein M is a Group 15 metal;

each R is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

y is 3,4 or 5, wherein n is less than y; and

each X is a halogen.

64. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RO)_nR′

_mX<sub>y−

(m+n)</sub>;

wherein M is a Group 15 metal,

each RO is a monovalent C₁ to C₃₀ hydrocarboxy radical independently selected from the group consisting of an alkoxy, aryloxy, arylalkoxy, alkylaryloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4;

y is 3,4 or 5, wherein the sum of n and m is less than y; and

each X is a halogen.

65. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is represented by the formula M(RC=OO)_nR′

_mX<sub>y−

(m+n)</sub>;

wherein M is a Group 15 metal;

each RC=OO is a monovalent C₂ to C₃₀ hydrocarbacyloxy radical independently selected from the group consisting of an alkacyloxy, arylacyloxy, arylalkylacyloxy, alkylarylacyloxy radicals;

each R′

is a monovalent C₁ to C₁₂ hydrocarbon radical independently selected from the group consisting of an alkyl, aryl, arylalkyl, alkylaryl and cycloalkyl radicals;

n is an integer from 0 to 4;

m is an integer from 0 to 4;

y is 3,4 or 5, wherein the sum of n and m is less than y; and

each X is a halogen.

66. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is independently selected from the group consisting of titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, zirconium tetrachloride, titanium bromide trichloride, titanium dibromide dichloride, vanadium bromide trichloride, tin chloride trifluoride, benzyltitanium trichloride, dibenzyltitanium dichloride, benzylzirconium trichloride, dibenzylzirconium dibromide, methyltitanium trichloride, dimethyltitanium difluoride, dimethyltin dichloride, phenylvanadium trichloride, methoxytitanium trichloride, n-butoxytitanium trichloride, di(isopropoxy)titanium dichloride, phenoxytitanium tribromide, phenylmethoxyzirconium trifluoride, methyl methoxytitanium dichloride, methyl methoxytin dichloride, benzyl isopropoxyvanadium dichloride, acetoxytitanium trichloride, benzoylzirconium tribromide, benzoyloxytitanium trifluoride, isopropoyloxytin trichloride, methyl acetoxytitanium dichloride, benzyl benzoyloxyvanadium chloride, vanadium oxytrichloride, aluminum trichloride, boron trifluoride, gallium trichloride, indium trifluoride, ethylaluminum dichloride, methylaluminum dichloride, benzylaluminum dichloride, isobutylgallium dichloride, diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, trimethylaluminum, triethylaluminum, methoxyaluminum dichloride, ethoxyaluminum dichloride, 2,6-di-tert-butylphenoxyaluminum dichloride, methoxy methylaluminum chloride, 2,6-di-tert-butylphenoxy methylaluminum chloride, isopropoxygallium dichloride, phenoxy methylindium fluoride, acetoxyaluminum dichloride, benzoyloxyaluminum dibromide, benzoyloxygallium difluoride, methyl acetoxyaluminum chloride, isopropoyloxyindium trichloride, antimony hexachloride, antimony hexafluoride, arsenic pentafluoride, antimony chloride pentafluoride, arsenic trifluoride, bismuth trichloride arsenic fluoride tetrachloride, tetraphenylantimony chloride, triphenylantimony dichloride, tetrachloromethoxyantimony, dimethoxytrichloroantimony, dichloromethoxyarsine, chlorodimethoxyarsine, difluoromethoxyarsine, acetatotetrachloroantimony, (benzoato) tetrachloroantimony, and bismuth acetate chloride.

67. The halogenated copolymer of claim 31, wherein the one or more Lewis acid(s) is independently selected from the group consisting of aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, methylaluminum dichloride, methylaluminum sesquichloride, dimethylaluminum chloride, boron trifluoride, and titanium tetrachloride.

68. The halogenated copolymer of claim 31, wherein the Lewis acid is not a compound represented by formula MX₃, where M is a group 13 metal, X is a halogen.

69. The halogenated copolymer of claim 31, wherein the one or more initiator(s) comprise a hydrogen halide, a carboxylic acid, a carboxylic acid halide, a sulfonic acid, an alcohol, a phenol, a polymeric halide, a tertiary alkyl halide, a tertiary aralkyl halide, a tertiary alkyl ester, a tertiary aralkyl ester, a tertiary alkyl ether, a tertiary aralkyl ether, an alkyl halide, an aryl halide, an alkylaryl halide or an arylalkylacid halide.

70. The halogenated copolymer of claim 31,wherein the one or more initiator(s) is independently selected from the group consisting of HCl, H₂O, methanol, (CH₃)₃CCl, C₆H₅C(CH₃)₂Cl, (2-Chloro-2,4,4-trimethylpentane) and 2-chloro-2-methylpropane.

71. The halogenated copolymer of claim 31, wherein the one or more initiator(s) is independently selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, acetic acid, propanoic acid, butanoic acid;

cinnamic acid, benzoic acid, 1-chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, p-chlorobenzoic acid, p-fluorobenzoic acid, acetyl chloride, acetyl bromide, cinnamyl chloride, benzoyl chloride, benzoyl bromide, trichloroacetylchloride, trifluoroacetylchloride, p-fluorobenzoylchloride, methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonyl chloride, methanesulfonyl bromide, trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonyl chloride, methanol, ethanol, propanol, 2-propanol, 2-methylpropan-2-ol, cyclohexanol, benzyl alcohol, phenol, 2- methylphenol, 2,6-dimethylphenol, p-chlorophenol, p-fluorophenol, 2,3,4,5,6- pentafluorophenol, and 2-hydroxynaphthalene.

72. The halogenated copolymer of claim 31, wherein the one or more initiator(s) is independently selected from the group consisting of 2-chloro-2,4,4-trimethylpentane;

2-bromo-2,4,4-trimethylpentane;

2-chloro-2-methylpropane;

2-bromo-2-methylpropane;

2-chloro-2,4,4,6,6-pentamethylheptane;

2-bromo-2,4,4,6,6-pentamethylheptane;

1 -chloro- 1-methylethylbenzene;

1 -chloroadamantane;

1 -chloroethylbenzene;

1,4-bis(1 -chloro- 1-methylethyl) benzene;

5 -tert-butyl- 1,3 -bis( 1 -chloro- 1 -methylethyl) benzene;

2-acetoxy -2,4,4-trimethylpentane;

2-benzoyloxy-2,4,4-trimethylpentane;

2-acetoxy-2-methylpropane;

2-benzoyloxy-2-methylpropane;

2-acetoxy-2,4,4,6,6-pentamethylheptane;

2-benzoyl-2,4,4,6,6-pentamethylheptane;

1 -acetoxy- 1-methylethylbenzene;

1 -aceotxyadamantane;

1 -benzoyloxyethylbenzene;

1,4-bis( 1-acetoxy- 1 -methylethyl) benzene;

5-tert-butyl- 1,3-bis( 1 -acetoxy- 1 -methylethyl) benzene;

2-methoxy-2,4,4-trimethylpentane;

2-isopropoxy-2,4,4-trimethylpentane;

2-methoxy-2-methylpropane;

2-benzyloxy-2-methylpropane;

2-methoxy-2,4,4,6,6-pentamethylheptane;

2-isopropoxy-2,4,4,6,6-pentamethylheptane;

1 -methoxy- 1 -methylethylbenzene;

1-methoxyadamantane;

1 -methoxyethylbenzene;

1 ,4-bis( 1 -methoxy- 1 -methylethyl) benzene;

5 -tert-butyl- 1,3 -bis(1 -methoxy- 1 -methylethyl) benzene, and 1,3,5 -tris( 1 -chloro 1 -methylethyl) benzene.

73. The halogenated copolymer of claim 31, wherein the one or more initiator(s) further comprise a weakly-coordinating anion.

74. The halogenated copolymer of claim 31, wherein the one or more initiator(s) comprise greater than 30 ppm water (based upon weight).

75. The halogenated copolymer of claim 31, wherein the contacting further comprises contacting one or more monomer(s) independently selected from the group consisting of olefins, alpha-olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenics, substituted styrenics, and vinyl ethers.

76. The halogenated copolymer of claim 31, wherein the contacting further comprises contacting one or more monomer(s) independently selected from the group consisting of styrene, para-alkylstyrene, para-methylstyrene, alpha-methyl styrene, divinylbenzene, diisopropenylbenzene, isobutylene, 2-methyl-l -butene, 3-methyl-l - butene, 2-methyl-2-pentene, isoprene, butadiene, 2,3-dimethyl- 1 ,3-butadiene, β

-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, methyl cyclopentadiene, piperylene, methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.